Quaternized nitrogen containing compounds

ABSTRACT

The invention relates primarily to quaternized compounds having the formula ##STR1## wherein n and n&#39; are each independently integers having a value of from 1 to 25; p is an integer having a value of from 1 to 4; Y and Y&#39; are each independently H or CH 3  ; R is linear alkyl, alkenyl, or amidoalkyl having from 8 to 22 carbon atoms and is optionally substituted with C 1  to C 4  alkyl; Z is linear alkylene having from 3 to 8 carbon atoms and is optionally substituted with lower alkyl and A -   is an anion.

This is a division of application Ser. No. 370,226, filed June 22, 1989.

In one aspect the invention relates to novel quaternized compounds whichpossess emulsifying, dye leveling, antistatic and fabric softeningproperties. In another aspect the invention relates to novel quaternizedcompounds having high compatability with anionic and non-ioniccomponents widely used in the formulation of cosmetic compositions suchas hair and skin care compositions. Still another aspect of theinvention relates to the preparation of said quaternized compounds andin still another aspect, the invention relates to the use of saidcompounds in several fields of application.

BACKGROUND OF THE INVENTION

The selection of components for hair and skin treating formulationspresents numerous difficulties involving compatibility. Several hairtreatment and shampoo formulations have been developed which aim toprovide conditioning action during cleansing so as to leave the hairsoft, manageable and lustrous and thus to eliminate a separateapplication of creme rinses or conditioning treatments. Problems arisefrom the limited compatibility of anionic detergents with commercialcationic conditioning agents which precipitate out of solution inshampoo formulations.

Shampoo formulations have employed conventional anionic surfactants suchas sodium lauryl sulfate, ammonium lauryl sulfate, ammonium lauryl ethersulfate and sodium lauryl ether sulfate which have been found to beincompatible with most cationic conditioning agents at effectiveconcentration levels.

Additionally, reproducible emulsifying media for polymerizationsrequiring product molecular weight control is often very difficult toachieve.

Accordingly it is an object of this invention to minimize or obviate theabove problems while providing additional benefits in hair and skintreating formulations.

Another object of the invention is to provide novel quaternized nitrogencontaining compounds having unique properties, particularly fabricsoftening and antistatic properties.

Another object is to provide novel quaternized nitrogen containingcompounds having excellent hair or skin conditioning properties whenincorporated into a shampoo or skin lotion and having high compatibilitywith components of hair and skin treating formulations.

Another object is to provide an economical and commercially feasiblemethod for the preparation of said novel quaternized nitrogen containingcompounds.

Still another object is to provide processes for the use of saidquaternized compounds.

These and other objects will become apparent from the followingdescription and disclosure.

THE INVENTION

According to this invention there is provided quaternized compoundshaving unique properties and defined by the formula ##STR2## wherein nand n' are each independently integers having a value of from 1 to 25; pis an integer having a value of from 1 to 4; and Y' are eachindependently H or CH₃ ; R is linear alkyl, alkylene or amidoalkylhaving from 8 to 22 carbon atoms and is optionally substituted with C₁to C₄ alkyl; Z is linear alkylene having from 3 to 8 carbon atoms and isoptionally substituted with lower alkyl and A⁻ is an anion. The anioncan be a chloride, bromide, iodide, sulfite, sulfate or sulfonate.

Preferred compounds within the above group are those wherein p is 1; Ris a tallow or coco moiety and Z is unsubstituted propylene or butylene.Examples of the pyrrolidonyl compounds of this invention include:

Bis-(2-hydroxyethyl) [(2-pyrrolidonyl)methyl] tallow ammonium salt

Bis-[2(2-hydroxyethoxy)ethyl] [2-pyrrolidonyl)methyl] tallow ammoniumsalt

Bis-(2-hydroxypropyl) [(2-pyrrolidonyl)methyl] coco ammonium salt

Bis-[2(2-hydroxypropoxy)propyl] [(2-pyrrolidonyl)ethyl] coco ammoniumsalt

Bis-hydroxyethoxylated quaternary of [(2-pyrrolidonyl)methyl] tallowamine

Bis-hydroxypropoxylated quaternary of [(2-pyrrolidonyl)methyl] tallowamine

Bis-hydroxyethoxylated quaternary of [(2-pyrrolidonyl)methyl] coco amine

Bis-hydroxypropoxylated quaternary of [(2-pyrrolidonyl)methyl] cocoamine

Bis-hydroxyethoxylated quaternary of [(2-pyrrolidonyl)methyl] dodecylamine

Bis-hydroxyethoxylated quaternary of [(2-pyrrolidonyl)methyl] octadecylamine

Bis-hydroxyethoxylated quaternary of [3(2-pyrrolidonyl)propyl]tetradecyl amine

Bis-hydroxyethoxylated quaternary of [2(2-pyrrolidonyl)ethyl] octadecylamine

It will be understood that compounds containing heterocyclic rings otherthan the pyrrolidonyl radical can be substituted in the above namedcompounds. Hence the corresponding piperidonyl, azacycloheptanonyl,azacyclononanonyl and azacyclodecanonyl equivalents of the abovecompounds are included within the scope of this invention.

The present quaternary compounds possess unique properties, among whichis their ability to form emulsions in the polymerization of acrylates.As additives in hair and skin conditioning formulations the presentproducts provide softening, antistatic and moisturizing properties andpossess high compatibility with anionic surfactants. In the context ofthis application, "conditioning" includes the functions of moisturizing,softening, cleansing, penetrating, disinfecting, luster enhancing, haircombability, thickening, dye retention and others. These compounds arehighly compatible with α-olefin sulfonates and anionic surfactant saltsconventionally employed in shampoos, skin lotions and textile treatingproducts. Their compatibility is such that up to 5% by weight or more ofthe quaternized compounds can be incorporated in the formulation, acharacteristic which permits the formation of effective formulations asliquids or gels. In contrast, most prior quaternary viscosity buildingconditioning compounds are incorporable only up to 0.5 or 1 wt. percentbased on total anionic formulations. It is contemplated that mixtures ofthe present quaternized compounds be employed in shampoos, hairconditioners, skin lotions and textile treating compositions as an agentwhich incorporates softening, thickening, scroop, conditioning andemulsifying qualities in one additive; thus eliminating the need forseparate chemical components to accomplish these individual needs. Thepresent compounds may also be used as dye levelors and penetratingagents in the treatment of fabrics or pelts. In applications, thequaternary compounds of this invention are generally mixed with astandard formulation of in an effective amount which can range frombetween about 0.05 to about 15% by weight, preferably between about 0.5and about 8% by weight, of the total formulation. The compatability ofthe present compounds with anionic α-olefin sulfonates is surprisingsince most anionic compounds cause precipitation of cationic agents.However, the present compounds in concentrations up to 5% by weight showno tendency to precipitate after extended periods including periods upto 6 months or more.

The quaternary pyrrolidonyl compounds of this invention are prepared byan economically feasible process which involves the reaction between analkyl amine containing at least 8 carbon atoms and a N-haloalkyl lactamhaving a 5 to 10 membered ring. A general equation for the preparationis defined by the equation: ##STR3## wherein n, n', p, R, Y, Y' and Zare as defined above, X is chloro, bromo or iodo and X⁻, derived fromthe haloalkyl pyrrolidone, can be ion exchanged with a tosylate or othersulfate or sulfite ion exchange compound to provide any of theaforementioned anion salts.

Examples of suitable lactam reactants include the N-chloromethyl,N-bromomethyl and N-iodomethyl derivatives of 2-pyrrolidone,4-methyl-2-pyrrolidone, 4-butyl-2-pyrrolidone, 2-piperidone,methyl-2-piperidone, 2-azacycloheptanone, 2-azacyclooctanone,2-azacyclononanone, 2-azacyclodecanone and other C₁ to C₄ alkylsubstituted derivatives bonded to an alkylene group in the heterocyclicring of these lactams. Mixtures of these lactam reactants can also beemployed to provide a correspondingly mixed quaternary product, ifdesired. Of these lactam reactants the N-halomethyl-2-pyrrolidones andN-halomethyl caprolactams are preferred and the N-chloromethyl lactamsare most preferred.

The tertiary alkyl diether amines employed in the present processinclude C₈ to C₁₈ alkyl ethoxylated or propoxylated speciescorresponding to the above product formula. The following 2 to 25 molespolyethoxylated or polypropoxylated amines are used: coco amine, tallowamine, decyl amine, dodecyl amine, tetradecyl amine, hexadecyl amine,octadecyl amine etc.

The process is effected under anhydrous conditions by reacting thetertiary alkyl ether amine and the haloalkyl lactam within a criticaltemperature range of between about 30° and 85° C. preferably betweenabout 40° and about 55° C., under a pressure of from about 0 to about 50psig, preferably atmospheric pressure, for a period up to about onehour; although usually not more than 30 minutes is required to completethe reaction. The temperature of reaction is closely controlled sincethe reaction is exothermic and, above 85° C., the product decomposes toform olefinic fatty acid by-products which are difficult and costly toremove.

From the above equation, it is seen that stoichiometric amounts ofhaloalkyl lactam and tertiary amine are used in the reaction. However,an excess of one or the other of the components is practicable in theprocess. Generally, for economic considerations, a mole ratio of between1:1.5 and about 1.5:1 is employed; although, a slight excess of thetertiary amine is recommended to insure complete reaction of the lactam.Accordingly, the most preferred mole ratio of lactam to amine is about1:1.01 and about 1:1.03.

It is also recommended that the haloalkyl lactam be added gradually ordropwise to the amine at the beginning of the exothermic reaction. Atthe completion of the reaction, the solid or viscous quaternized productis recovered. Since the reaction is quantitative, the product can beused as is or, when a slight excess of the amine is employed, it can beneutralized with a weak acid such as acetic, lactic or citric acid,depending on the ultimate use of the product.

For incorporating into a standard formulation of shampoo, cream rinse,hand or body lotion, dye bath or textile treating formulation, etc., thepresent product can be diluted with an inert diluent such as water,propylene glycol, ethanol, etc. The solution in the desiredconcentration can then be mixed into the formulation to provide ahomogeneous liquid, gel, cream or lotion. However, since the presentproducts in solvents are generally liquid at room temperature, they maybe directly incorporated into a formulation. Incorporation of thepresent product is usually affected at room temperature underatmospheric pressure and requires no special formulating technique.However, for certain formulations incorporation of the present productcan be effected at temperatures up to about 85° C. and below thedecomposition temperature of the product. Amphoteric-containing shampooformulations are best prepared by initially preparing an aqueoussolution of the quaternized product and the amphoteric surfactant andthen adding the solution to the shampoo or skin treating formulation.

Having generally described the invention, reference is now had to theaccompanying examples which set forth preferred embodiments, but whichare not to be construed as limiting to the scope of the invention asmore broadly set forth above and in the appended claims.

EXAMPLE 1

To a 1-liter, 4-neck flask equipped with mechanical stirrer, refluxcondenser, thermometer, and dropping funnel is added bis-[hydroxyethyl]tallow amine (87.1 g, 0.253 mole) which is heated with stirring to 40°C. under N₂ blanket after which the heating source is removed andN-chloromethyl-2-pyrrolidone (33.4 g, 0.25 mole) is added to the aminedropwise over a period of 10 minutes. An exothermic reaction ensues andis controlled to between 70°-80° C. by the rate of addition ofN-chloromethyl-2-pyrrolidone. The reaction mixture becomes viscousduring the addition of the N-chloromethyl-2-pyrrolidone and remains as aviscous liquid on completion of the reaction. The yield of liquidbis(2-hydroxyethyl) [(2-pyrrolidonyl)methyl] tallow ammonium chloride isquantitative. The content of quaternized product is determined bytitration. (Mercuric Acetate method as described by Sidney Siggia,"Quantitative Organic Analysis via Functional Group", 1963, 3d Ed., JohnWiley & Sons, pages 552-554).

EXAMPLES 2-7

Example 1 is repeated except that the amines noted in following Table Iare substituted for N,N-di(hydroxyethyl) tallow amine. The results ofthese synthesis reactions are as shown in Table I.

                  TABLE I                                                         ______________________________________                                                       Moles of  Moles of                                                            EO* in    Poly Ethoxy-                                                                           Moles of                                                                             %                                    Example                                                                              Amine   the Amine lated Amine                                                                            lactam Yield                                ______________________________________                                        2      Tallow  5         0.505    0.5    99                                   3      Tallow  10        1.01     1      98.5                                 4      Tallow  20        1.01     1      98                                   5      Coco    2         0.505    0.5    99.5                                 6      Coco    10        0.505    0.5    99.5                                 7      Coco    10        0.505    0.5    98.5                                 ______________________________________                                         *EO = ethylene oxide                                                     

EXAMPLE 8

The reaction of Example 1 is repeated except that the amine used ispolyethoxylated (5 moles) dodecyl amine (2% molar excess with respect toN-chloromethyl-2-pyrrolidone). The product, bis-hydroxyethoxylated (5moles) quaternary chloride of [(2-pyrrolidonyl)methyl] dodecyl amine isneutralized with acetic acid and recovered in quantitative yield.

EXAMPLE 9

The reaction of Example 1 is repeated except that the polyethoxylated(10 moles) octadecyl amine and N-chloromethyl-2-piperidone issubstituted for bis-hydroxyethyl) tallow amine andN-chloromethyl-2-pyrrolidone. The corresponding bis-hydroxyethoxylated(10 moles) quaternary chloride of [(2-piperidonyl)methyl] octadecylamine product is recovered in substantially quantitative yield.

EXAMPLE 10

The quaternized ammonium chloride product of Example 1 (49.0 g) isreacted with p-toluene sulfonic acid sodium salt (19.4 g) for 1 hour at50° C. The corresponding p-toluene sulfonate salt was recovered in 95%yield.

EXAMPLE 11

    ______________________________________                                        SHAMPOO FOR OILY HAIR                                                         Ingredients        Parts by Weight                                            ______________________________________                                        Compound No. 2 in Table I                                                                        4.0                                                        tetrasodium ethylenediamine                                                   tetra-acetic acid  0.2                                                        sodium lauryl sulfate                                                                            20.0                                                       alpha-olefin sulfonate                                                                           20.0                                                       polyquaternium 11  0.5                                                        deionized water    qs                                                         preservative       qs                                                         colorant           qs                                                         fragrance          qs                                                         added inorganic salts as desired for viscosity                                modification                                                                  ______________________________________                                    

EXAMPLE 12

    ______________________________________                                        HAIR CONDITIONER                                                              Ingredients        Parts by Weight                                            ______________________________________                                        Compound No. 3 in Table I                                                                        4.0                                                        PEG-8 Distearate   2.5                                                        mineral oil        1.5                                                        lanolin alcohol    1.0                                                        stearic acid       1.0                                                        PPG-20 methyl glucose ether                                                                      1.0                                                        hydrolized animal protein                                                                         0.25                                                      citric acid to pH  4                                                          deionized water    qs                                                         preservative       qs                                                         fragrance          qs                                                         ______________________________________                                    

EXAMPLE 13

    ______________________________________                                        CONDITIONING SHAMPOO                                                          Ingredients        Parts by Weight                                            ______________________________________                                        Compound 6 in Table I                                                                            3.0                                                        N-dodecyl-2-pyrrolidone                                                                          0.6                                                        polyquaternium 11  0.5                                                        sodium laureth-4-phosphate                                                                       0.8                                                        ammonium lauryl sulfate                                                                          40.0                                                       silk protein        0.25                                                      tetrasodium ethylenediamine                                                   tetra-acetic acid  0.2                                                        deionized water    qs                                                         colorant           qs                                                         fragrance          qs                                                         ______________________________________                                    

The compounds employed in the formulations of Examples 11-13 provided asignificant softening effect on the hair and improved glossiness.

EXAMPLE 14

    ______________________________________                                        MOISTURIZING LOTION                                                           Ingredients        Parts by Weight                                            ______________________________________                                        Compound No. 5 in Table I                                                                        2.0                                                        mineral oil 70 CTS 2.0                                                        stearic acid       3.0                                                        emulsifying wax    3.0                                                        Dimethicone* 200 CTS                                                                             1.5                                                        Carbomer 934**      0.15                                                      Oleth-20***        1.0                                                        triethanolamine 98%                                                                              1.0                                                        deionized water    qs                                                         preservative       qs                                                         fragrance          qs                                                         ______________________________________                                         *a mixture of methylated siloxane polymers endblocked with trimethyl          siloxy units (dimethylpolysiloxane)                                           **crosslinked polymer of acrylic acid                                         ***PEGether of oleyl alcohol                                             

What is claimed is:
 1. The process of synthesizing the compound havingthe formula ##STR4## wherein n and n' are each independently integershaving a value of from 1 to 25; p is an integer having a value of from 1to 4; Y and Y' are each independently H or CH₃ ; R is linear alkyl,alkenyl, or amidoalkyl having from 8 to 22 carbon atoms and isoptionally substituted with C₁ to C₄ alkyl; Z is linear alkylene havingfrom 3 to 8 carbon atoms and is optionally substituted with lower alkyland A⁻ is an anion which comprises reacting under anhydrous conditions aN-haloalkyl lactam of the formula ##STR5## with a slight excess of atertiary amine having the formula ##STR6## wherein p, Z, R, Y, Y', n andn' are as defined and X is a halogen atom; said reaction being carriedout under a pressure of from about 0 to about 50 psig and at atemperature not in excess of 85° C. to produce the correspondingaddition product as a quaternized ammonium halide and optionallyreacting said quaternized ammonium halide with a sulfate or sulfonateion exchange agent to provide the corresponding sulfate or sulfonatesalt.
 2. The process of claim 1 wherein the reaction temperature isbetween about 40° C. and about 55° C.
 3. The process of claim 1 whereinsaid haloalkyl lactum is N-chloromethyl-2-pyrrolidone.
 4. The process ofclaim 1 wherein n and n' in said tertiary amine each have a value offrom 2 to 20 and R is a tallow or a coco radical.